Chemical products for adhesive applications

ABSTRACT

The embodiments described herein generally relate to methods and chemical compositions for coating substrates with a composition. In one embodiment, an adhesive composition is provided comprising a reaction product of a polyacid selected from the group consisting of an aromatic polyacid, an aliphatic polyacid, an aliphatic polyacid with an aromatic group, and combinations thereof, or a diglycidyl ether; and a polyamine; and one or more compounds selected from the group consisting of a branched aliphatic acid, a cyclic aliphatic acid with a cyclic aliphatic group, a linear aliphatic, and combinations thereof. The adhesive composition may be used to cover a substrate.

RELATED APPLICATION DATA

This application claims benefit to U.S. Provisional Application No.62/353,444, filed Jun. 22, 2016, of which the entire contents of theapplication are incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to compositions and products in variousapplications requiring tackiness. The present invention particularlyrelates to compositions and products for reducing or mitigating theproduction of dust from the handling of substrates, and also for finescontrol, flow-back control, and conductivity enhancements in hydraulicfracturing operations.

BACKGROUND

During hydraulic fracturing when sand is pumped into the formation, asignificant amount of fines that are generated at different stages ofsand processing and handling are also pumped into the formation with thesand. These fines will migrate to restrict the conductive path that isformed by the sand, and reduce the conductivity of the path.

Proppant flowback is another common problem in fracture stimulatedwells. Proppant flowback results in increased well maintenance costs anddecreased well production for the productive life of the well. The mostcommon way to reduce proppant flowback is to use curable resin coatedproppant (RCP), which has been used for over 30 years. However, RCPshave higher cost compared to uncoated proppant, there can be erosion ofresin coating during loading/off loading of the RCPs, and customersoften end of paying for unused RCP on location.

Another way to reduce proppant flowback is to make the proppant surfacesticky. Tacky chemicals are added to the dry proppant in the fracblender and screw sand hopper at an adjustable concentration to reduceproppant flowback. The tacky chemicals cost less than traditional RCP,eliminate RCP coating erosion, and allow customers to pay for only theproppant coated and pumped downhole. This technology can also be appliedin remote locations and use locally sourced substrates where RCP is notreadily available. However, current tacky chemicals for proppants havehigh tackiness at room temperature, which can result in cloggingequipment and wellbores during operation.

Additionally, dust generation is problematic in sand mining, storage,transportation and pumping on the frac sites. Dust control is a verychallenging problem, and the U.S. Department of Labor's OccupationalSafety and Health Administration (OSHA) provides regulations forlimiting the occupational exposure to dust particles such as crystallinesilica.

Currently, dust control, depending on operation, mainly involves wettingwith water, using binders such as lignin sulfonate and processed ligninproducts, bitumens, tars, and resinous adhesives. All the coatings usedin the frac sand in the prior art involve polymeric resins. However,coating the surface of sand with polymers normally involves complexcompositions (polymers are normally prepared in emulsion) andprocedures. Another drawback with polymer coatings is that thesepolymers normally have high glass transition temperature, which makesthe coating layer brittle, and easily susceptible to mechanicaldegradation which can generate a secondary dust that is potentiallyexplosive.

Additionally dust control problems affect other industries havingparticulate issues including mining, such as coal or sand, sandprocessing, construction, road building, agricultural processes, andgeneral environmental issues.

It would be desirable if compositions and methods could be devised thatwould adhere the fines to the sand, and prevent fines migration andaggregation, thus, preserve the conductivity of the channels, or to havea resin that can be delivered in a solvent or emulsion, with the coatinglayer remaining inherently flexible as compared to the prior art.

SUMMARY

The embodiments described herein generally relate to methods andchemical compositions for coating substrate with an adhesivecomposition. In one embodiment, a composition is provided comprising areaction product of a polyacid selected from the group consisting of anaromatic polyacid, an aliphatic polyacid, an aliphatic polyacid with anaromatic group, and combinations thereof, or a diglycidyl ether; and apolyamine; and one or more compounds selected from the group consistingof a branched aliphatic acid, a cyclic aliphatic acid with a cyclicaliphatic group, a linear aliphatic acid, and combinations thereof.

In one embodiment, an adhesive composition is provided comprising areaction product of a polyacid selected from the group consisting of anaromatic polyacid, an aliphatic polyacid, an aliphatic polyacid with anaromatic group, and combinations thereof, or a diglycidyl ether; and aC2-C18 polyamine; and one or more compounds selected from the groupconsisting of a branched aliphatic acid having C2-C26 alkyl group, acyclic aliphatic acid with C7-C30 cyclic aliphatic group, a linearaliphatic acid having C2-C26 alkyl group, and combinations thereof.

In another embodiment, a particulate material is provided, including asubstrate and an adhesive composition including a reaction product of apolyacid selected from the group consisting of an aromatic polyacid, analiphatic polyacid, an aliphatic polyacid with an aromatic group, andcombinations thereof, or a diglycidyl ether; and a polyamine; and one ormore compounds selected from the group consisting of a branchedaliphatic acid, a cyclic aliphatic acid with a cyclic aliphatic group, alinear aliphatic, and combinations thereof. In another embodiment, agravel pack is provided including the particle material.

In another embodiment, a process for forming a proppant is provided,including providing a substrate, and disposing an adhesive compositionthereon.

The features, functions, and advantages that have been discussed can beachieved independently in various embodiments or may be combined in yetother embodiments, further details of which can be seen with referenceto the following description and drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the features, advantages and objects of theinvention, as well as others which will become apparent, are attained,and can be understood in more detail, more particular description of theinvention briefly summarized above may be had by reference to theembodiments thereof which are illustrated in the appended drawings thatform a part of this specification. It is to be noted, however, that thedrawings illustrate only a preferred embodiment of the invention and aretherefore not to be considered limiting of its scope as the inventionmay admit to other equally effective embodiments.

FIG. 1 is a graph showing the comparison of viscosity of sand slurrycoated with Sample 1 of this invention versus uncoated sand as acontrol;

FIG. 2 is a graph showing the viscosity of sand slurry coated withSample 1 of this invention at different temperature control;

FIG. 3 is a graph showing the impact of solvent on UCS value of thecoated proppant core; and

FIG. 4 is a graph showing the UCS value of proppant core coated withcross-linked adhesive of this invention.

DETAILED DESCRIPTION

Embodiments of the invention are compositions for coating substrates. Inone embodiment, a particulate material is formed by coating a substratematerial with an adhesive composition. In one embodiment, a compositionis generally considered adhesive when the composition before or afterapplication exhibits adhesive strength above 1 N/m² or work of adhesionabove 1 J/m².

The substrate material may be any organic or inorganic particulatematerial.

Suitable inorganic particulate materials include inorganic materials (orsubstrates), such as exfoliated clays (for example, expandedvermiculite), exfoliated graphite, blown glass or silica, hollow glassspheres, foamed glass spheres, cenospheres, foamed slag, sand, naturallyoccurring mineral fibers, such as zircon and mullite, ceramics, sinteredceramics, such as sintered bauxite or sintered alumina, othernon-ceramic refractories such as milled or glass beads, and combinationsthereof. Exemplary inorganic substrate materials may be derived fromsilica sand, milled glass beads, sintered bauxite, sintered alumina,mineral fibers such as zircon and mullite, or a combination comprisingone of the inorganic substrate materials.

Suitable organic particulate materials include organic polymermaterials, naturally occurring organic substrates, and combinationsthereof. The organic polymer materials may comprise any of the polymericmaterials described herein that are carbon-based polymeric materials.Another particulate material is dust, which can be organic or inorganicdepending on the source material from which it is derived.

Naturally occurring organic substrates are ground or crushed nut shells,ground or crushed seed shells, ground or crushed fruit pits, processedwood, ground or crushed animal bones, or a combination comprising atleast one of the naturally occurring organic substrates. Examples ofsuitable ground or crushed shells are shells of nuts such as walnut,pecan, almond, ivory nut, brazil nut, ground nut (peanuts), pine nut,cashew nut, sunflower seed, Filbert nuts (hazel nuts), macadamia nuts,soy nuts, pistachio nuts, pumpkin seed, or a combination comprising atleast one of the foregoing nuts. Examples of suitable ground or crushedseed shells (including fruit pits) are seeds of fruits such as plum,peach, cherry, apricot, olive, mango, jackfruit, guava, custard apples,pomegranates, watermelon, ground or crushed seed shells of other plantssuch as maize (e.g., corn cobs or corn kernels), wheat, rice, jowar, ora combination comprising one of the foregoing processed wood materialssuch as, for example, those derived from woods such as oak, hickory,walnut, poplar, mahogany, including such woods that have been processedby grinding, chipping, or other form of particalization. An exemplarynaturally occurring substrate is a ground olive pit.

The substrate may also be a composite particle, such as at least oneorganic component and at least one inorganic component, two or moreinorganic components, and two or more organic components. For example,the composite may comprise an organic component of the organic polymericmaterial described herein having inorganic or organic filler materialsdisposed therein. In a further example, the composite may comprise aninorganic component of any of the inorganic polymeric material describedherein having inorganic or organic filler materials disposed therein.

Inorganic or organic filler materials include various kinds ofcommercially available minerals, fibers, or combinations thereof. Theminerals include at least one member of the group consisting of silica(quartz sand), alumina, mica, meta-silicate, calcium silicate, calcine,kaoline, talc, zirconia, boron, glass, and combinations thereof. Fibersinclude at least one member selected from the group consisting of milledglass fibers, milled ceramic fibers, milled carbon fibers, syntheticfibers, and combinations thereof.

The substrate material may have any desired shape such as spherical, eggshaped, cubical, polygonal, or cylindrical, among others. It isgenerally desirable for the substrate material to be spherical in shape.Substrate materials may be porous or non-porous. Preferred substrateparticles are hard and resist deforming. Alternatively, the substratematerial may be deformable, such as a polymeric material. Deforming isdifferent from crushing wherein the particle deteriorates usuallycreating fines that can damage fracture conductivity. In one embodiment,the inorganic substrate material does not melt at a temperature below450° F. or 550° F.

For proppant formation, the substrate may be in the form of individualparticles that may have a particle size in the range of ASTM sieve sizes(USA Standard Testing screen numbers) from about 6 to 200 mesh (screenopenings of about 3360 μm or about 0.132 inches to about 74 μm or 0.0029inches). Typically for proppant or gravel pack individual particles ofthe particulate substrate have a particle size in the range of USAStandard Testing screen numbers from about 8 to about 100 mesh (screenopenings of about 2380 μm or about 0.0937 inches to about 150 μm orabout 0.0059 inches), such as from 20 to 80 mesh (screen openings ofabout 841 μm or about 0.0311 inches to about 177 μm or 0.007 inches),for example, 40 to 70 mesh, (screen openings of about 400 μm or about0.0165 inches to about 210 μm or 0.0083 inches) may be used to definethe particle size.

In one embodiment of the invention, the proppant material size is 20/40mesh, 30/50 mesh, 40/70 mesh, 70/140 mesh (commonly referred to as “100mesh”). A size of a 20/40 mesh is commonly used in the industry as amaterial having a size between a 20 mesh and 40 mesh as describedherein. Smaller mesh proppants, such as 40/70 mesh proppants, may beused in low viscosity fracture fluids, and larger mesh proppants, suchas 20/40 mesh proppants, may be used in high viscosity fracture fluids.

In one embodiment, the adhesive composition includes a reaction productof a polyacid and a polyamine; and one or more compounds selected fromthe group consisting of a branched aliphatic acid having C2-C26 alkylgroup, a cyclic aliphatic acid with C7-C30 cyclic aliphatic group, alinear aliphatic acid having C2-C26 alkyl group, and combinationsthereof. The reaction product of a polyacid and a polyamine forms anadduct.

The polyamine may be any amine having two or more amine groups. Suitablepolyamines include diamines. Suitable diamines includepolyethylenepolyamines, C2-C12 linear diamines, cyclic diamines, diaminewith aromatic content, polyetherdiamines, polyoxyalkylene diamines, andcombinations thereof. Examples of diamines include diamines selectedfrom the group consisting of ethylenediamine, diethylenetriamne,triethylenetetraamine, bis(aminomethyl)cyclohexane, phenylenediamine,naphthalene diamine, xylene diamine, polypropylene oxide diamine, andcombinations thereof. Other suitable amines include higher amines fromreactions of diamines such as xylenediamine with epichlorohydrin such asGaskamine 328 (Mitsubishi Gas Chemical Co). Other polyamines includetriamines and tetramines, for example, polyethertriamine (JeffamineT-403 available from Huntsman of Houston Tex.) and triethylenetetramine(TETA), and combinations thereof.

In one embodiment of the polyamines, a diamine is selected from thegroup consisting of polyethylenepolyamines, C2-C12 diamines,polyetherdiamines, and combinations thereof. Examples of these diaminesinclude diamines selected from the group consisting of ethylenediamine,diethylenetriamne, triethylenetetraamine, and combinations thereof.

The reaction product includes from about 10 wt. % to about 60 wt. %,such as from about 15 wt. % to about 45 wt. %, of the polyamine; andfrom about 40 wt. % to about 90 wt. %, such as from about 55 wt. % toabout 85 wt. % of the polyacid based on the weight of the reactionproduct. The polyamine and the polyacid may also be provided to form thereaction mixture at a molar ratio of polyamine to polyacid of about 2:1to about 1:2.

The polyacid may be selected from the group consisting of an aromaticpolyacid, an aliphatic polyacid, an aliphatic polyacid with an aromaticgroup, and combinations thereof.

The polyacid may comprise a diacid. Suitable diacids include diacidsselected from the group consisting of aromatic diacid, aliphatic diacid,aliphatic diacid with an aromatic group, and combinations thereof. Thediacids may be saturated diacids or unsaturated diacids. The diacids mayalso be C2-C24 diacids and/or dimerized fatty acids. Suitable examplesof diacids include terephthalic acid, phthalic acid, isophthalic acid,oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,pimelic acid, suberic acid, azelaic acid, maleic acid, fumaric acid,muconic acid, and combinations thereof.

The aliphatic diacid with aromatic group(s) block(s) between the acidgroups may be represented by following general formulas:

and combinations thereof, wherein each of R1 and R2 are independentfunctional groups selected from the group consisting of C1-C12 alkyl,alkanoxy, alkylamino, and alkylcaroboxy, and each of R3, R4, R5, and R6are independent functional groups selected from the group consisting ofhydroxyl (—OH), amino, nitro, sulfonyl, C1-C12 alkyl, alkanoxy,alkylamino, and alkylcaroboxy.

The aromatic diacids may also be substituted with a functional groupselected from the group consisting of amine, hydroxyl (—OH), C1-C12alkyl, alkylamino, alkanoxy, alkylenoxy, alkylcarboxy, alkylnitro,alkylsulfonyl, and wherein the substitution on the aromatic ring is inone or more positions. For example, the terephthalic acid, the phthalicacid, and the isophthalic acid, may be substituted with a functionalgroup selected from the group consisting of amine, hydroxyl (—OH),C1-C12 alkyl, alkylamino, alkanoxy, alkylenoxy, alkylcarboxy,alkylnitro, alkylsulfonyl, and wherein the substitution on the aromaticring is in one or more positions.

In one embodiment, the adhesive composition includes a reaction productof a triacid and a polyamine; and one or more compounds selected fromthe group consisting of a branched aliphatic acid having C2-C26 alkylgroup, a cyclic aliphatic acid with C7-C30 cyclic aliphatic group, alinear aliphatic acid having C2-C26 alkyl group, and combinationsthereof. The reaction product of the triacid and the polyamine forms anadduct.

Suitable triacid include citric acid, isocitric acid, aconitic acid,propane-1,2,3-tricarboxylic acid, trimesic acid, and the combinationsthereof.

In one embodiment, the adhesive composition includes a reaction productof a tetraacid and a polyamine; and one or more compounds selected fromthe group consisting of a branched aliphatic acid having C2-C26 alkylgroup, a cyclic aliphatic acid with C7-C30 cyclic aliphatic group, alinear aliphatic acid having C2-C26 alkyl group, and combinationsthereof. The reaction product of the tetracid and the polyamine forms anadduct.

Suitable tetraacids include ethylenediaminetetraacetic acid (EDTA),furantetracarboxylic acid, methanetetracarboxylic acid,ethylenetetracarboxylic acid, benzenetetracarboxylic acid, andbenzoquinonetetracarboxylic acid, and the combinations thereof.

In another embodiment, the adhesive composition includes a reactionproduct of a polyamine and a diglycidyl ether; and one or more compoundsselected from the group consisting of a branched aliphatic acid havingC2-C26 alkyl group, a cyclic aliphatic acid with C7-C30 cyclic aliphaticgroup, a linear aliphatic acid having C2-C26 alkyl group, andcombinations thereof. The reaction product of the diglycidyl ether andthe polyamine forms an adduct.

The reaction product includes from about 10 wt. % to about 60 wt. %,such as from about 15 wt. % to about 45 wt. %, of the polyamine, andfrom about 40 wt. % to about 90 wt. %, such as from about 55 wt. % toabout 85 wt. %, of the diglycidyl ether based on the weight of thereaction product. The polyamine and the diglycidyl ether may also beprovided to form the reaction mixture at a molar ratio of polyamine todiglycidyl ether of about 2:1 to about 1:2.

Examples of suitable diglycidyl ether selected from the group consistingof diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F,diglycidyl ether of bisphenol B, diglycidyl ether of bisphenol C,diglycidyl ether of bisphenol E, diglycidyl ether of bisphenol AP,diglycidyl ether of bisphenol AF, diglycidyl ether of bisphenol BP,diglycidyl ether of bisphenol G, diglycidyl ether of bisphenol M,diglycidyl ether of bisphenol S, diglycidyl ether of bisphenol P,diglycidyl ether of bisphenol PH, diglycidyl ether of bisphenol TMC,diglycidyl ether of bisphenol Z, and combinations thereof.

In another embodiment, the adhesive composition includes a reactionproduct of a polyamine and a diacid, a diglycidyl ether, or acombination thereof; and one or more compounds selected from the groupconsisting of a branched aliphatic acid having C2-C26 alkyl group, acyclic aliphatic acid with C7-C30 cyclic aliphatic group, a linearaliphatic acid having C2-C26 alkyl group, and combinations thereof. Thereaction product of the a polyamine and a diacid, a diglycidyl etherforms an adduct.

The reaction product includes from about 10 wt. % to about 80 wt. %,such as from about 18 wt. % to about 50 wt. %, of the polyamine, andfrom about 20 wt. % to about 90 wt. %, such as from about 50 wt. % toabout 82 wt. %, of the diacid, the diglycidyl ether, or a combinationthereof based on the weight of the reaction product. The polyamine andthe diacid, diglycidyl ether may also be provided to form the reactionmixture at a molar ratio of polyamine to the diacid, the diglycidylether, or a combination thereof of about 2:1 to about 1:2.

The composition may comprise from about 25 wt. % to about 96 wt. %, suchas from about 45 wt. % to about 80 wt. %, of the reaction product andmay comprise from about 4 wt. % to about 75 wt. %, such as from about 20wt. % to about 55 wt. % of the one or more compounds selected from thegroup consisting of a branched aliphatic acid having C2-C26 alkyl group,a cyclic aliphatic acid with C7-C30 cyclic aliphatic group, a linearaliphatic acid having C2-C26 alkyl group, and combinations thereof.

The polyamine and the diglycidyl ether may also be provided to form thereaction mixture at a molar ratio of polyamine to the diacid, thediglycidyl ether, or a combination thereof of about 2:1 to about 1:2,with the one or more compounds selected from the group consisting of abranched aliphatic acid having C2-C26 alkyl group, a cyclic aliphaticacid with C7-C30 cyclic aliphatic group, a linear aliphatic acid havingC2-C26 alkyl group, and combinations thereof being added to thecomposition at a molar ratio of polyamine to the diacid, the diglycidylether, or a combination thereof to the one or more compounds of about2:2:1 to about 2:6:5. For example, an aliphaticacid-amine-diacid-amine-aliphatic acid structure, has a molar ratio of2:2:1 ratio, and an aliphatic acid-(amine-diacid)₅-amine-aliphatic acidhas a structure with a molar ratio of 2:6:5 ratio.

The branched aliphatic acid having a C2-C26 alkyl group may be selectedfrom the group consisting of neopentanoic acid, neononanoic acid,neodecanoic acid, neotridecanoic acid, and combinations thereof.Examples of such acids include Hexion's Versatic™ Acid 5, 9, 10, 913,and 1019 acids. The branched aliphatic acid having a C2-C26 alkyl groupmay comprise from about 9 wt. % to about 65 wt. %, such as from about 25wt. % to about 50 wt. %, of the composition.

The cyclic aliphatic acid with C7-C30 cyclic aliphatic group may beselected from the group consisting of rosin, naphthenic acid, andcombinations thereof. Examples of rosins include rosin acid, tall oilrosin, or gum rosin. All rosins are provided the CAS number 8050-09-7.The cyclic aliphatic acid with C7-C30 cyclic aliphatic group maycomprise from about 20 wt. % to about 87 wt. %, such as from about 25wt. % to about 65 wt. %, of the composition.

The linear aliphatic acid having C2-C26 alkyl group may be selected fromthe group consisting of unsaturated C2-C26 fatty acids, saturated C2-C26fatty acids, and combinations thereof. Examples of unsaturated fattyacids include tall oil fatty acid, myristoleic acid, palmitoleic acid,sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid,linoelaidic acid, alpha-linolenic acid, arachidonic acid,eicosapentaenoic acid, erucic acid, docosahexaenoic acid, andcombinations thereof. Examples of saturated fatty acids include caprylicacid, capric acid, lauric acid, myristic acid, palmitic acid, stearicacid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, andcombinations thereof. The linear aliphatic acid having C2-C26 alkylgroup may be any plant and animal fatty acid that are the combinationsof above unsaturated and saturated fatty acids such as tall oil fattyacid, rosin acid, and fatty acids made from chicken fat, lard, beeftallow, canola oil, flaxseed oil, sunflower oil, corn oil, olive oil,sesame oil, peanut oil, cottonseed oil, palm oil, butter, and cocoabutter, palm kernel oil, coconut oil, and the alike. One example is talloil fatty acids, and another example is rosin acid. The linear aliphaticacid having C2-C26 alkyl group may comprise from about 20 wt. % to about87 wt. %, such as from about 25 wt. % to about 65 wt. %, of thecomposition.

In one embodiment of the invention, the adhesive composition is madewith the diacid comprising terephthalic acid, the polyamine comprisingdiethylenetriamine, and the linear aliphatic acid having C2-C26 alkylgroup comprising tall oil fatty acid (TOFA). Such a composition issuitable for use as a dust control composition, among other uses.

In one embodiment of the invention, the adhesive composition is madewith the diacid comprising terephthalic acid, the polyamine comprisingdiethylenetriamine, and the cyclic aliphatic acid with C7-C30 cyclicaliphatic group comprises rosin. Such a composition is suitable for useas a proppant flow-back control composition in fracturing process, amongother uses.

In one embodiment of the invention, the adhesive composition is madewith the diacid comprising terephthalic acid, the polyamine comprisingdiethylenetriamine, and the cyclic aliphatic acid with C7-C30 cyclicaliphatic group comprises rosin. Such a composition, when combined witha cross-linking agent, is suitable for use as a proppant flow-backcontrol and consolidating agent for proppant pack and gravel pack infracturing process, among other uses.

In one embodiment of the invention, the adhesive composition is madewith the diacid comprising terephthalic acid, the polyamine comprisingdiethylenetriamine, and the cyclic aliphatic acid with C7-C30 cyclicaliphatic group comprises rosin. Such a composition, when combined witha cross-linking agent, is suitable for use as agents for consolidatingdownhole formation of the well in fracturing process, among other uses.

In another embodiment, a cross-linking agent may be added to thecomposition. The cross-linking agents may include epoxy compounds.Examples of suitable cross-linking agents include a diglycidyl etherselected from the group consisting of diglycidyl ether of bisphenol A,diglycidyl ether of bisphenol F, diglycidyl ether of bisphenol B,diglycidyl ether of bisphenol C, diglycidyl ether of bisphenol E,diglycidyl ether of bisphenol AP, diglycidyl ether of bisphenol AF,diglycidyl ether of bisphenol BP, diglycidyl ether of bisphenol G,diglycidyl ether of bisphenol M, diglycidyl ether of bisphenol S,diglycidyl ether of bisphenol P, diglycidyl ether of bisphenol PH,diglycidyl ether of bisphenol TMC, diglycidyl ether of bisphenol Z, andcombinations thereof. For example, diglycidyl bisphenol ether may beused as a cross-linking agent for R-diamine-diacid-diamine-R typeadhesives. In another example, the diglycidyl bisphenol ether also canbe used to form R-diamine-diglycidyl bisphenol ether-diamine-R typeadhesive.

In one embodiment, the adhesive composition comprises a formula selectedfrom the group of:

R₁-dAm-(dAc-dAm_(n)R₂  (Structure 1),

R₁-dAm-(dGE-dAm_(n)R₂  (Structure 2),

or a mixture thereof, wherein n is 0 to 10, R1 and R2 are eachindependently selected from the group of a branched aliphatic acidhaving C2-C26 alkyl group, cyclic aliphatic acid with C7-C30 cyclicaliphatic group, a linear aliphatic acid having C2-C26 alkyl group, or acombination thereof, the dAm comprises a polyamine, such a diaminedescribed herein, dAc comprises a diacid as described herein, and dGecomprises a diglycidyl ether as described herein.

In another embodiment, the diacid comprises terephthalic acid, thepolyamine comprises diethylenetriamine, and the reaction productcomprises:

the reaction product is then reacted with (a branched aliphatic acidhaving C2-C26 alkyl group) versatic acid, (the cyclic aliphatic acidwith C7-C30 cyclic aliphatic group) rosin (Rosin), (the linear aliphaticacid having C2-C26 alkyl group) tall oil fatty acid (TOFA), or acombination thereof and the composition comprises:

In another embodiment, the adhesive composition includes a reactionproduct from concurrently reacting components a)-c) which are a) apolyamine, b) a diacid, a diglycidyl ether, or a combination thereof,and c) one or more compounds selected from the group consisting of abranched aliphatic acid having C2-C26 alkyl group, a cyclic aliphaticacid with C7-C30 cyclic aliphatic group, a linear aliphatic acid havingC2-C26 alkyl group, and combinations thereof. The reaction product ofa), b), and c) forms a composition.

In another embodiment, the adhesive composition comprises a formulaselected from the group of:

Wherein R′ is the central organic segment of a diacid (HO₂C—R′—CO₂H) asdescribed herein. R₁ and R₂ are each independently selected from thegroup of a branched aliphatic acid having C2-C26 alkyl group, cyclicaliphatic acid with C7-C30 cyclic aliphatic group, a linear aliphaticacid having C2-C26 alkyl group, or a combination thereof. R₃ and R₄ arealkyl, or alkylamino groups such as —(CH₂—)_(n)—, or —(CH₂CH₂NH)_(n)—,or combination thereof and n is from 0 to 10. Structure 5 is abis-imidazoline component. Structure 5 is derived from a diacid(HO₂C—R′—CO₂H) as described herein with R′ being the organic segment towhich the carboxylic acid groups are attached.

The composition described herein for Structures 1, 2, 4, and 5 canfurther be modified by grafting the backbone through oxyalkylation ofthe secondary amine, or reacting the secondary amine with ethyleneoxide, propylene oxide or butylene oxide in any ratio, or sequences, ormolar mass.

The composition described herein for Structures 1, 2, 4, and 5 canfurther be modified by reacting the secondary amine with epoxides.Suitable epoxides include an alkylglycidyl ether, such as butylglycidylether, p-tert-butyl phenyl glycidyl ether, cresyl glycidyl ether, castoroil glycidyl ether, glycidyl ester of neodecanoic acid, and combinationsthereof.

The composition described herein for Structures 1, 2, 4, and 5 canfurther be modified by grafting the main chain through amidation of thesecondary amine, or through the esterification of the hydroxyl withcarboxylic acids if there are hydroxyl groups available for reaction.Suitable carboxylic acids include any carboxylic acids described hereinincluding, for example, tall oil fatty acid, tallow fatty acid,neoalkanoic acid (such as Hexion's Versatic™ acid described herein), andcombinations thereof.

The composition described herein for Structures 1, 2, 4, and 5 canfurther be modified by quaterizing the secondary amine. Suitablecompounds for quaterizing the secondary amine include, but not limitedto, benzyl chloride, acrylic acid, and combinations thereof.

The composition described herein for Structures 1, 2, 4, and 5 canfurther be reacted by oxidizing the secondary amine to an amine oxide.

The adhesive composition may further comprise a solvent. Suitablesolvents include a solvent selected from the group consisting ofaromatic solvents, ethers, alcohols, water, and combinations thereof.Examples of aromatic solvents include toluene, xylenes, naphthas, andcombinations thereof. Examples of suitable naphtha solvents are heavyaromatic naphtha solvents such as Aromatic 100, Aromatic 150, andAromatic 200, commercially available from ExxonMobil Inc. Examples ofethers include diglyme, triglyme, polyglyme, proglyme (BASF), ethyleneglycol butyl ether (EGBE), tripropyleneglycol methyl ether,ethyleneglycol butyl ether, dipropylene glycol ethyl ether, tripropyleneglycol ethyl ether, diethylene glycol ethyl ether, diethyleneglycolbutyl ether, and combinations thereof. Examples of alcohols includemethanol, isopropanol, ethanol, propanol, butanol, ethoxytriglycol,methoxytriglycol, 2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane (Solvay SL191), and combinations thereof.

The solvent system or solvent mixture is designed to allow transport anddelivery of the coating material at the individual interfaces betweenthe individual sand grains. These solvent combinations are also designedto allow good solubility and good wetting of the sand surface. Thesolvent system is designed to have a water soluble component orcomponents that assist transport and delivery of the coating material inthe slurry, but diffuse into the aqueous matrix after coating to allow aviscous, adhesive coating on the sand surface. The subsequent diffusionof the oil soluble component or components from the coating layer intothe oil matrix ensures a rigid adhesive bond between the sand grains andconsequently the formation of a solid core.

The adhesive compositions herein may function as a pressure sensitiveadhesive when the composition is in a (high viscosity) liquid state orsemi-liquid state. In one embodiment, the composition may furtherinclude solvents, plasticizers, wetting agents, polymers, andcombinations thereof.

The adhesive composition described herein may be used for coating aproppant, used for adhesive applications, such as a tackifier forhot-melt adhesive applications, or pressure sensitive adhesive, used forpaints and other large surface coatings. Additionally, the adhesivecoating may are used for dust suppression, such as in agricultural,coal, stone (gravel dust), cement, concrete, and road applications,among others. In fracturing processes, the adhesive composition may beused for proppant flow-back control, the consolidation of proppantpacks, and consolidation of formations, among other uses.

A process for forming an adhesive composition includes reacting a diacidand a polyamine to form a reaction mixture, and then adding one or morecompounds selected from the group consisting of a branched aliphaticacid having C2-C26 alkyl group, a cyclic aliphatic acid with C7-C30cyclic aliphatic group, a linear aliphatic acid having C2-C26 alkylgroup, and combinations thereof, to form the adhesive composition.

In one embodiment of the process, the adhesive composition may becreated as follows. A diacid and a polyamine are added together in areactor at a first temperature and then heated to a second temperature.The reaction was continued at the second temperature for a first periodof time until no water was further released and the reaction product wasformed. Optionally, a nitrogen purge may be performed during the firstperiod of time. Then the one or more compounds selected from the groupconsisting of a branched aliphatic acid having C2-C26 alkyl group, acyclic aliphatic acid with C7-C30 cyclic aliphatic group, a linearaliphatic acid having C2-C26 alkyl group, and combinations thereof, toform the adhesive composition, were added to the reactor and thereaction was continued at the second temperature for a second period oftime. The one or more compounds may be added dropwise. Optionally, anitrogen purge may be performed during the second period of time. Thereaction temperature was increased to a third temperature for a thirdperiod of time. After the third period of time, the composition wascooled to a fourth temperature, and transferred to a receptacle, whichwas maintained at a fifth temperature.

The first temperature was from about 100° C. to about 185° C., forexample, from about 145° C. to about 180° C. The second temperature wasfrom about 0.180° C. to about 220° C., for example, from about 190° C.to about 215° C. The first period of time was from about 30 minutes toabout 5 hours, for example about 1.5 hours. The second period of timewas from about 30 minutes to about 5 hours, for example about 1 hour.The third temperature was from about 210° C. to about 260° C., forexample, about 250° C. The third period of time was from about 20minutes to about 3 hours, for example about 30 minutes. The fourthtemperature was from about 260° C. to about 140° C., for example, about150° C. The fourth temperature was from about 150° C. to about 110° C.,for example, about 120° C.

In one embodiment, the particle material may be a proppant materialformed by coating a substrate material as described herein with theadhesive composition described herein.

Proppant materials, or proppants, are generally used to increaseproduction of oil and/or gas by providing a conductive channel in theformation. Fracturing of the subterranean formation is conducted toincrease oil and/or gas production. Fracturing is caused by injecting aviscous fracturing fluid or a foam at a high pressure (hereinafterinjection pressure) into the well to create a fracture. A similar effectcan be achieved by pumping a thin fluid (water containing a lowconcentration of polymer) at a high injection rate.

As the fracture is formed, a particulate material, referred to as a“proppant” is placed in the formation to maintain the fracture in apropped condition when the injection pressure is released. As thefracture forms, the proppants are carried into the fracture bysuspending them in additional fluid or foam to fill the fracture with aslurry of proppant in the fluid or foam, often referred to as a frackingfluid. Upon release of the pressure, the proppants form a pack thatserves to hold open the fractures. The propped fracture thus provides ahighly conductive channel in the formation. The degree of stimulationafforded by the hydraulic fracture treatment is largely dependent uponformation parameters, the fracture's permeability, the propped fracturelength, propped fracture height and the fracture's propped width.

Gravel packing treatments are used to reduce the migration ofunconsolidated formation sands/fines into the well bore. In gravelpacking operations, the proppant materials described herein aresuspended in a carrier fluid and are pumped into a well bore in whichthe gravel pack is to be placed. The carrier fluid leaks off into thesubterranean zone and/or is returned to the surface while the proppantmaterials are left in the annulus between the production string and thecasing or outside the casing in the subterranean zone adjacent to thewellbore.

Gravel pack operations generally involve placing a gravel pack screen inthe well bore and packing the surrounding annulus between the screen andthe well bore with the particles. The gravel pack screen is generally atype of filter assembly used to support and retain the proppantmaterials placed during the gravel pack operation. A wide range of sizesand screen configurations are available to suit the characteristics of aparticular well bore, the production fluid, and the subterraneanformation sands. Such gravel packs may be used to stabilize theformation while causing minimal impairment to well productivity. Thegravel pack acts as a filter to separate formation sands from producedfluids while permitting the produced oil and/or gas to flow into thewell bore. The proppant materials act to prevent formation sands fromplugging the screen or migrating with the produced fluids, and thescreen acts to prevent fines from being produced to the surface and outof the well.

In some situations the processes of hydraulic fracturing and gravelpacking are combined into a single treatment to provide stimulatedproduction and an annular gravel pack to reduce formation sandproduction. Such treatments are often referred to as “frac pack”operations. In some cases, the treatments are completed with a gravelpack screen assembly in place, and the hydraulic fracturing treatmentbeing pumped through the annular space between the casing and screen. Insuch a situation, the hydraulic fracturing treatment usually ends in ascreen out condition creating an annular gravel pack between the screenand casing. This allows both the hydraulic fracturing treatment andgravel pack to be placed in a single operation.

In one embodiment, the particle material may be a proppant formed bycoating a substrate material as described herein with the adhesivecomposition described herein. The deposited coating may be continuous ornon-continuous. If continuous, the coating may be deposited at athickness from about 0.001 microns to about 10 microns. The proppantmaterial may be pre-cured or curable.

In one embodiment of the proppant material, the coating of the adhesivecomposition may comprise from about 0.05% to about 10% by weight, suchas from about 0.5% to about 4% by weight, for example, from about 0.8%to about 2% by weight, of the proppant material; and the substratematerial comprises from about 90% to about 99.95% by weight, such asfrom about 95% to about 99.9% by weight, for example, from about 98% toabout 99.8% by weight, of the proppant material.

The process to form the proppant material may be a batch process, asemi-continuous process, or a continuous process. The process to formthe proppant material may be performed remotely at a manufacturingfacility or may be manufactured at point of use, such as using a devicedescribed in United States Patent Publication US2015/0360188, which isincorporated herein by reference in its entirety not inconsistent withthe description herein.

In one embodiment of the proppant formation process, a substratematerial, such as sand, introduced into a mixing device. The substratematerial may be heated before or after addition to a mixing device. Thesubstrate material is heated to a temperature from about 20° C. to about50° C., for example, about 21° C. Next the adhesive composition, and anyadditives, such as a coupling agent or cross-linking agent, are addedwhile mixing. After a coating period of time, such as from about 1minute to about 1 hour, for example about 4.25 minutes, the batch iscooled through the addition of water and mixing continued to obtainfree-flowing particles of coated proppant. The coated particles(proppant material) are discharged from the mixer and pass through ascreen and the desired particle sizes of proppant are recovered. Theparticles are agitated during curing.

In another embodiment of the proppant formation process, the proppantmay be a formed by a real-time coating or point-of-use manufacturingprocess, such as at a well site. In such a process, a substratematerial, such as sand, is introduced into a mixing device. Next theadhesive composition, and any additives, such as a coupling agent orcross-linking agent, are added while mixing. After a coating period oftime, such as from about 1 minute to about 1 hour, for example about4.25 minutes, the coated substrate will be directly delivered to thefracturing fluid, and pumped together to the down-hole formation.

The mixing can take place in a device that uses shear force, extensionalforce, compressive force, ultrasonic energy, electromagnetic energy,thermal energy or a combination comprising at least one of the foregoingforces and energies. The mixing is conducted in processing equipmentwherein the aforementioned forces are exerted by a single screw,multiple screws, intermeshing co-rotating or counter rotating screws,non-intermeshing co-rotating or counter rotating screws, reciprocatingscrews, screws with pins, barrels with pins, screen packs, rolls, rams,helical rotors, or a combination comprising at least one of theforegoing. Exemplary mixing devices are EIRICH™ mixer, WARING™ blenders,HENSCHEL™ mixers, BARBER GREEN™ batch mixers, ribbon blenders, or thelike.

In an embodiment of a proppant production process, substrate material iscoated in a continuous system. Substrate material enters an elongated(for example, 20 feet long) horizontal mixer containing two horizontallymounted shafts having paddles to promote mixing the ingredients andmoving them horizontally along the mixer. If employed, any additives,such as a coupling agent or cross-linking agent, are immediately added,and then the adhesive composition as described herein is added. Thismixture travels down the mixer. The total time in the mixer can rangefrom about 3-10 minutes depending on desired throughput rate.

In one embodiment of a continuous coating system in which substratematerial and coating material are fed to the long horizontal orientedmixer that may be of varying length and diameter. The embodiment of thecontinuous coating system has from two to four horizontal shafts thatrun the length of the mixer. Along the shaft there are positionedmultiple sets of mixing paddles mounted on the shaft. The paddles areoriented so as to insure both mixing and the transport of the substratefrom the beginning of the mixer to its exit point. At various pointsalong the mixer are positioned addition ports so chemicals may be addedat prescribed rates and times. For example, there may be addition portsfor additives and surface wettability modifiers as described herein.

The proppant materials, as described in this invention may be injectedinto the subterranean formation as the sole proppant in a 100% proppantpack (in the hydraulic fracture) or as a part replacement of existingcommercial available ceramic and/or sand-based proppants, polymericmaterial-coated and/or uncoated, or as blends between those, forexample, coated particles, are 5 to 50 weight % proppant materials asdescribed herein of the total proppants injected into the well. Forexample, the uncoated proppant materials may be first placed in a well,and afterwards a proppant material as described herein may be placed inthe fracture that is closest to the wellbore or fracture openings. Thistype of fracturing treatment is done without stopping to change theproppant and is known in the industry as a “tail-in treatment”.

In a further embodiment, proppant materials as described herein in the70/140 mesh range, sometimes referred to as fluid loss additives, areprovided as a part replacement of existing commercial available ceramicand/or sand-based proppants, polymeric material-coated and/or uncoated,or as blends between those, are 3 to 50 weight % proppant materials asdescribed herein of the total proppants. Such 70/140 mesh proppantmaterials described herein would be placed first, typically as part of apad. This portion of the coated proppant is typically pumped in slugs inthe pad.

In another embodiment, the adhesive composition described herein may bedirectly added to a fracturing fluid (also referred to as fracking fluidor carrier fluids). Generally, fracturing fluids are well known in theart of examples of materials comprising fracturing fluids includegelling agent, friction reducer, acids, surfactants, water, andcombinations thereof. The adhesive composition described herein may bepresent in an amount in the range of from about 0.05 weight percent toabout 10 weight percent, such as from about 0.5 weight percent to about3 weight percent based on the total weight of the fracturing fluid.

For dust control, the adhesive composition described herein may beapplied to suppress dust on substrates, which may also be referredherein to as dust source substrate. The composition may be disposed onthe substrate, and may be applied to be continuously orsemi-continuously disposed on the dust source substrate. The compositionmay be applied on one or more substrates, as described herein above asorganic or inorganic particulate material comprising the dust sourcesubstrate, such as for coal contained in a coal car. Suitable dustsource substrates to which the composition can be applied include coal(and coal dust), mined materials including ores and minerals, surfacemining operations, roads and road surfaces including unimproved roadsand surfaces (for example “dirt roads”), mining or manufacturing wastedumps, harvested and non-harvested agricultural crops, fields, charcoal,sand mines, sand transloads, proppant transloads, sand storage, proppantstorage, earth moving operations, cement mixing, open railcar loads,open truck loads, environmental remediation, quarries, mining waste,wind erosion protection, agriculture product control (crop seeds dustcontrol), and soil stabilization, and combinations thereof, amongothers. For example, in one embodiment, the compositions may be appliedto a substrate of coal as a coal dust suppressant. The compositiondescribed herein may also be used as a topical spray on automobiles as aproactive coating for shipment.

The adhesive composition described herein may be applied to a dustproducing substrate or substrates, such as coal which produces coaldust. The composition may be applied to the exposed surfaces, such as atop surface, of the substrate, such as coal, by applying thecompositions described herein by a spraying technique, a mistingtechnique, a poring technique, mixing technique, blending technique orcombinations thereof, to the exposed surfaces of the substrate. Thecomposition or emulsions described herein are applied to providesufficient dust suppression. The composition described herein may bediluted or emulsified prior to application to a substrate or used with asolvent, and may be combined with water or solvent. In one embodiment,the composition may be applied to provide for dust control at an amountof 0.001 to 10 wt. % of the weight of the substrates.

EXAMPLES

Aspects and advantages of the embodiments described herein are furtherillustrated by the following examples. The particular materials andamounts thereof, as well as other conditions and details, recited inthese examples should not be used to limit the embodiments describedherein. All parts and percentages are by weight unless otherwiseindicated.

Example 1: Typical Synthesis Procedure of the Adhesives

To a four-neck flask was charged diethylenetriamine (DETA, 51.5 g, 0.5mol). The flask was heated up to 145° C. Terephthalic acid (TPA, 41.5 g,0.25 mol) was charged portion wise so no clumping occurs, while allowingthe heating to continue. The temperature was controlled between 145° C.to 180° C. After the addition was complete, and TPA was completelydissolved, the reaction was heated up to 190-215° C., and held at thistemperature for 1.5 h, or until no water was further released. Nitrogenpurge was used to drive the reaction to complete. To the flask was addedtall oil fatty acid (TOFA) (L-5 from Ingevity, 148 g, 0.5 mol) dropwise, and the reaction continued. The addition took about 1 h. After theaddition was complete, the reaction was held at 190° C. to 215° C. for 1h. Nitrogen purge was used to drive the generated water out. Thereaction was then heated up to 250° C., and held for 30 min. Thereaction was then cooled down to 150° C., and the liquid brown productwas transferred to a glass jar.

Example 2: Flow-Back Control Coating-Stickiness Evaluation

A new test method was developed to evaluate the degree of adhesion(tackiness) that the chemicals of this invention introduce to thesurface of the individual sand grains when they are coated with thechemicals. The equipment of this new method was designed and constructedthat the viscosity of the slurry can be measured at various temperaturesbetween 0° C. and 95° C., using a circulated water bath with accuratetemperature control. The coating procedure is as the following.

Sample 1, made by the process of Example 1 except using rosin in placeof the tall oil fatty acid to form the final product, was dissolved in asolvent comprising of 25% heavy aromatic naphtha and 75%dipropyleneglycol ether to generate a viscous liquid with 50% activeingredient. 1 g of the liquid sample was added to 100 g of sand in a 200ml glass jar, and the resulting mixture was mixed with a spatulamanually for 5 min, or until the chemical was evenly coated on the sandsurface. Next, 100 ml of tap water was added to the jar, and theresulting slurry was stirred with a spatula manually for 20 seconds, andthe water was decanted. The last step was repeated once. Then, 60 ml oftap water were added to the jar.

The increase in viscosity of the slurry, as result of the chemicaladdition is used as an indication of the degree of adhesion (stickiness)between the sand grains. The viscosity of the slurry was measured with aBrookfield viscometer, equipped with T-bar spindles, which was immersedin the slurry during the measurement.

From FIG. 1 (FIG. 1), sand coated with the adhesive of this inventionhas significantly higher viscosity at all rotational rates, especiallyat the 5 and 10 RPM.

A major challenge in fracturing operation that uses the real-timecoating method is that the high stickiness of the coating layer causesclogging of equipment and wellbore. In order to reduce the clogging, anideal coating layer should have low stickiness at ambient temperaturewhen coated sand is pumped to down-hole formation, while having ormaintaining good stickiness after depositing in the down-hole fractureswhich normally has high temperature and high pressure (HPHT or HTHP).From FIG. 2 (FIG. 2), Sample 1 provides a good temperature profileappreciable to one of ordinary skilled in the art. At ambienttemperature when the coated sand is pumped, Sample 1 has a relativelylow viscosity, and at high temperature that corresponds to the down-holecondition, the viscosity remains stable to one of ordinary skilled inthe art.\

Example 3. Flow-Back Control Coating-Evaluation of UnconfinedCompressive Strength of Non-Cross-Linked Resin

Unconfined Compressive Strength—general loading and testing procedure.

The terms “cured” and “curable” may be defined for the presentspecification by the bond strength of the surface material. In oneembodiment described herein, curable is any surface material having aUCS Bond Strength of 1 psi or greater and/or capable of forming a core.

Compressive strength of curable proppants is defined as that measuredaccording to the following procedure, known as the UnconfinedCompressive Strength or UCS test. In this test, proppant is added to a 2weight percent KCl solution doped with a small amount of detergent toenhance wettability. The KCl solution and proppant, such as from about 6to about 18 lbs., typically about 12 lbs. proppant per gallon KCl, aregently agitated to wet the proppant. Remove entrained air bubbles, ifany. If necessary use a wetting agent to remove the bubbles. This slurryfrom about 100 to about 200 grams (depending on density) is transferredinto duplicate 1.25 inch outside diameter, 10 inch stainless steelcylinders, equipped with valves on the top and bottom to bleed liquidand gas pressure as required, a pressure gauge reading 0 to 2000 psi,and a floating piston to transfer pressure to the sample. Typically atleast 2, preferably at least 3 specimen molds are loaded to give alength greater than two times the diameter of the finished slug. Thebottom valve is opened during the application of stress, allowing fluidto drain from the slurry, and then closed during the application oftemperature. The cylinder is connected to a nitrogen cylinder and 1000psi is imposed on the cylinder, transmitted by the sliding pistons tothe sample, and then the top valve is shut and the bottom valve remainsopen.

As the test temperature is approached near to the fluid valve on themold, the bottom valve (fluid valve) is closed. Closing the fluid valvetoo soon may generate enough pressure, as the cell is heating, toprevent/reduce the intended closure stress applied to the proppant slug.Closing the valve too late may allow loss of too much fluid from theslug by evaporation or boiling. The duplicate cylinders containing thesample are transferred to an oven preheated to the desired setpoint, forexample, 200° F., and remain in the oven for 24 hours. Maintain stressand temperature during the cure time. Stress should be maintained +−10%.During the curing process in the oven, loose curable proppant particlesbecome a consolidated mass. At the end of the 24 hours, the cylindersare removed, venting off pressure and fluid rapidly, and theapproximately one inch by six inch consolidated slug sample is pressedfrom the cylinder. The sample is allowed to cool and air dry for about24 hours, and cut (typically sawed) into compression slugs of lengthtimes diameter (L×D) of greater than 2:1, preferably about 2.5:1. Airdrying is performed at a temperature of less than about 49° C. (120°F.). Typically, both ends of each slug are smoothed to give flatparallel surfaces and the slugs are cut to maintain a greater than 2:1ratio of the length:diameter.

The compression slugs are mounted in a hydraulic press and force isapplied between parallel platens at a rate of about 4000 lbs_(f)./minuteuntil the slug breaks. For slugs with compressive strength less than 500psi, use a loading rate of about 1000 lbs_(f)./minute. The forcerequired to break the slug is recorded, replicates are documented, andthe compressive strength for each sample is calculated using the formulabelow. An average of the replicates is used to define the value for thisresin coated proppant sample. The formula for calculation isFc=(4*Fg)/((p*d²)*(0.88+(0.24 d/h))) with Fc=compressive strength (psi),Fg=hydraulic gauge reading (lb force), p=pi (3.14), d=diameter of theslug (inches), and h=length of slug (inches).

Compressive strength of the slugs is determined using a hydraulic press,such as a Carver Hydraulic Press, model #3912, Wabash, Ind. Typicalcompressive strengths of proppants of the present invention range fromabout 10 to about 100 psi or higher. However, the reproducibility of theUCS test is probably +−10% at best. It is also noted that theCompressive Strength Test can be used to indicate if a coating is curedor curable. No bonding, or no consolidation of the coated particles,following wet compression at 1000 psi at 200° F. for a period of as muchas 24 hours, indicates a cured material.

The molded specimens made according to this procedure are suitable formeasurement of Brazilian tensile strength and/or unconfined compressivestrength (UCS) test of ASTM D 2938-91 or ASTM D 2938-95 Standard TestMethod for Unconfined Compressive Strength of Intact Rock CoreSpecimens. For compressive strength measurements, the test specimenshall be cut to a length of at least 2.25 inches (57.2 mm), a length todiameter ratio of at least 2 to 1, and then broken according to ASTM D2938-91 Standard Test Method for Unconfined Compressive Strength ofIntact Rock Core Specimens. For Brazilian tensile strength measurements,the test specimen shall be cut to a length of at least 0.56 inch (14.2mm) but not more than 0.85 inch (21.6 mm), a length to diameter ratio ofat least 0.5-0.75 to 1, according to ASTM D 3967-92 Standard Test Methodfor Splitting Tensile Strength of Intact Rock Core Specimens.

Samples 2-8 were prepared according to following procedure: 8 g of aselected adhesive made by using the typical synthetic procedure inExample 1 by replacing TOFA with S-rosin (CAS number 8050-09-7), wasdissolved in 8 g of a selected solvent system listed in Table 1 at roomtemperature. S-Rosin is a rosin product commercially available fromIngevity Inc. of Charleston, S.C.

TABLE 1 Solvent used for each sample (all with 10% methanol)* sample 240DPM/50A150 sample 3 50DPM/40A150 sample 4 60DPM/30A150 sample 565DPM/25A150 sample 6 70DPM/20A150 sample 7 75DPM/15A150 *DPM =dipropylenemethyl ether, A150 is ExxonMobil's Aromatic 150 solvent

Samples 2-8 were coated and loaded to the UCS cell according tofollowing procedure: To a beaker containing 200 g 40/70 mesh Hi-crushsand was added 4 g (2%) of the above liquid, and resulting mix wasstirred with a spatula vigorously for 5 to 10 minutes, or until thechemical was evenly coated on the sand surface (no visible chemical dropleft). To the beaker was added 139 g of 2% KCl solution, and theresulting mixture was mixed vigorously with a spatula for 5 to 10minutes. The sand slurry was then loaded on a UCS cell following thegeneral loading procedure described above. The cell is then transferredto an oven and maintained at 200° F. for 24 h. The cell was then movedfrom the oven, and the core extracted.

The core was then dried in a dehumidifying chamber for at least 24 hours(h) before measuring the unconfined compressive strength. The resultsare shown on FIG. 3 (FIG. 3).

For conventional resin coated proppant, the UCS value is normally in50-300 scale. It is obvious that adhesives of this invention provideoutstanding UCS value, which is comparable to some resin coatedproppants. Also, the solvent system seems to have impact to the UCSvalue, samples 3 and 5 seem to be the best one.

Example 4. Curable Coating for Flow-Back Control and Consolidation ofProppant Pack—Formulation and Evaluation of Unconfined CompressiveStrength of Cross-Linked Resin

The active adhesive compositions of samples 8, 9, 10, and 11 were madeby using the typical synthetic procedure in Example 1 with thestoichiometry as shown in Table 2.

TABLE 2 Sample Molar Ratios Samples Molar Ratios 8 terephthalicacid:DETA:rosin = 1:2:2 9 terephthalic acid:DETA:rosin = 2:3.5:3 10terephthalic acid:DETA:rosin:TOFA = 1:2:1:1 11 terephthalicacid:DETA:TOFA = 1:2:2

Samples 8, 9, 10, and 11 are formulated according to the followingprocedure. 8 g of a selected adhesive was dissolved in 8 g of a solventcombination (25% Aromatic 150 and 75% dipropylene glycol methyl ether)at room temperature. 2 g of Hexion's EPON™ Resin 828 was added to thesolution, and the resulting mixture was mixed with a spatula thoroughlyto a homogeneous liquid.

To a beaker containing 200 g 40/70 mesh Hi-crush sand was added 4 g (2%)of the above liquid, and resulting mix was stirred with a spatulavigorously for 5 to 10 minutes, or until the chemical is evenly coatedon the sand surface (no visible chemical drop left). To the beaker wasadded 139 g of 2% KCl solution, and the resulting mixture was mixedvigorously with a spatula for 5 to 10 minutes. The sand slurry was thenloaded on a UCS cell following the general loading procedure describedabove. The cell was then transferred to an oven and maintained at 200°F. for 24 h. The cell was then moved from the oven, and the coreextracted. The core was then dried in a dehumidifying chamber for atleast 24 h before measuring the unconfined compressive strength. Theresults are shown on FIG. 4 (FIG. 4).

From FIG. 4, samples 8 and 9 provided better UCS values than Sample 11.It indicates rosin derivative is better than TOFA for UCS. However, whenthe adhesive was made with the mixture of rosin and TOFA (Sample 10).The UCS value is as good as sample 8 and 9. Generally, the four samplesall provided outstanding UCS values.

Example 5. Performance of Chemicals of this Invention on Dust Control

The following experiments are for the demonstration of dust Controlproperty of the adhesives of this invention.

Ball Milling Test Method.

The dust levels of particles can be determined for particles subjectedto a Ball Mill Test using a Turbidity Test. The particles are processedin the Ball Mill as follows. Into a standard eight inch ball mill, threeceramic balls (about 2 inches in diameter) are added along with 150grams of the material to be tested. This combination is closed andplaced on the rollers at about 50 rpm. The unit is stopped at specifictimes, samples removed, and subjected to the Turbidity Test as describedbelow. After being subjected to the Ball Mill Test, the particles aresubjected to a Turbidity Test as follows.

Turbidity Test Method.

Equipment used was a Hach Model 2100P turbidity meter with Gelexsecondary standards and a Thermolyne Maxi-Mix 1 vortex mixer. Theturbidity test was performed on 5 gram samples using as reagents of 15grams of deionized/distilled water, doped with 0.1% FSO surfactant orFS-34 surfactant and 15 grams of DuPont™ ZONYL® FSO Fluorosurfactant orDuPont™ Capstone® FS-34.

Samples are measured according to the following steps: 1) Weigh 5.00grams of the sample to be measured and place this in the cell from step4 above; 2) Using the Vortex mixer, agitate the sample/water mixture for30 seconds; 3) Clean the outside of the cell with lint free paper; 4)Place the sample/cell back into the turbidimeter and read the turbidity,30 seconds after the Vortex mixing ended; and 5) Record the turbidity inNTU units for this sample as “dust content”.

The Ball Mill Test is assumed to simulate the likely amount of dustgenerated during transportation and pneumatic transfer. The amount ofdust generated is measured via the Turbidity Test.

Unconfined Compressive Strength was done according to the generalprocedure described in the previous paragraph.

Test Data is shown below in the Table 3.

Sample 12 was formed by dissolving the reaction product of terephthalicacid, diethylenetriamne and TOFA in an equal amount of a solvent mixture(25% aromatic 150 (heavy aromatic naphtha from ExxonMobil), and 40%2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane (Solvay SL 191) and 10%methanol).

Sample 13 was formed by dissolving the reaction product of terephthalicacid, diethylenetriamne and TOFA in an equal amount of a solvent mixture(25% aromatic 150 (heavy aromatic naphtha from ExxonMobil), and 75%polyglyme (polyglycol methyl ether)).

All below experiments follow the general procedure described in the nextparagraph with variations at loading dosage, and coating temperature.

For ambient and above temperature coating examples, the process employs1 kg of 100 mesh sand with a single layer coating of Sample 12. The sandwas transferred to a Littleford lab mixer. The mixer agitator wasstarted and the sand was heated to a temperature of 70° F. andmaintained at that temperature with a heat gun. Once the temperature wasachieved, 2 grams of Sample A was added at the start of the mixingprocess. After a total mixing time of 4 minutes and 15 seconds themixing was stopped, the coated material was passed through a no. 30 USmesh sieve, then Ball Milling test was performed on the coated materialto check for dust suppression and the product was tested for 24 hour UCSbond strength at 1000 psi and 200° F.

For below ambient temperature coating examples, the process employs 1 kgof 100 mesh sand with a single layer coating of Sample 13. The sand waschilled in a freezer to 33° F. for 24 hours and transferred to aLittleford lab mixer. The mixer agitator was started and 4 grams ofSample 1 was added at the start of the mixing process. After a totalmixing time of 4 minutes and 15 seconds the mixing was stopped, thecoated material was passed through a no. 30 US mesh sieve, thenTurbidity test was performed on the coated material to check for dustsuppression and the product was tested for 24 hour UCS bond strength at1000 psi and 200° F.

TABLE 3 Test Results of Samples 12 and 13 Turbidity (NTU) for PercentageCoating Ball Milling Times (min) UCS of Coating Temperature 0 15 30 4560 (U/C) Entry Sample (g/100 g sand) (° F.) (min) (min) (min) (min)(min) U/C 1 Control 0 70 386 678 1156 1674 1904 U 2 Sample 0.2 70 16.1242 391 643 983 C 12 3 Sample 0.2 130 11.8 144 287 512 843 U 12 4 Sample0.4 70 22.3 57.1 133 99.3 135 C 12 5 Sample 0.4 130 11.9 81.0 468 8881000 C 12 6 Sample 0.6 70 27.4 43.2 53.1 69.5 89.9 C 12 7 Sample 0.6 13014.0 81.5 174 269 167 C 12 8 Sample 0.4 33 17.7 N/A N/A N/A N/A U 12 9Sample 0.1 70 26.0 360 846 1000 1000 C 12 10 Sample 0.1 70 40.6 287 6381000 1000 C 13 11 Sample 0.2 70 43.1 198 340 788 1000 C 13 12 Sample 0.4130 28.0 36.5 51.4 112 121 C 13 13 Sample 0.4 3 20.5 N/A N/A N/A N/A C13 U = Unconsolidated UCS core, C = Consolidated UCS core, but nomeasurable strength

Table 3 illustrates test results of the examples identified before thetable, and a sample of uncoated 100-mesh sand used as a control. Thecolumns labeled; Turbidity (NTU) for Ball Milling Times (min),illustrated different dust levels of the particles when subjected to aball milling over time. The API turbidity requirement is 250 NTU. Priorto ball mill testing, the initial turbidity of the control, uncoated100-mesh sand, exceeded the API turbidity requirement of 250 NTU. Whenthe control was ball milled the dust levels increased with time. Theturbidity of the control nearly tripled after 30 minutes, and after 60minutes, the turbidity was nearly five times the initial turbidity. TheBall Mill data showed how well the dust levels minimized with theaddition of a coating. Entries 4 and 12 are good examples in showing howthe coating reduce the turbidity of 100-mesh sand and kept the turbidityrelatively low (below API turbidity requirement) even after subjected tothe ball mill for 60 minutes. The Ball Mill Tests were an attempt tosimulate the effects of the mechanical abrasion associated with proppanttransfer such as trucking, rail, belt travel, and pneumatic transfer.Another column labeled; UCS (U/C), illustrated consolidation. The samplewould or would not consolidate under conditions explained earlier insection; Unconfined Compressive Strength. Many of the coated samplesconsolidated and could possibly conclude that the sample might ofdemonstrated particle-to-particle bonding and could offer flow-backcontrol for downhole conditions, unlike the control.

Table 3 illustrates some of the test results found from the examplesthat are identified before the table and uncoated 100 mesh sand for acontrol. The first group of test results labeled; Turbidity (NTU),showed the different dust levels of the particles for particlessubjected to a Ball Mill Test using a Turbidity Test for coated anduncoated examples. The table also shows how the dust levels couldpossibly change over a period of time when subjected to a Ball Mill. ATurbidity Test is used to measure that change from the initial; which isprior to Ball Milling, and up to 60 minutes of Ball Milling. A readingwould be taken in 15 minute increments to display a trend. From thistest you could possibly conclude how well a coated or uncoated examplewould minimize the dust levels through harsh handling and transport ofthe sample. Additional dust can be generated when product is transportedto its final destination due to mechanical abrasion. Ball mill testswere conducted to simulate the effects of mechanical abrasion associatedwith product transfer such as trucking, rail, belt travel, and pneumatictransfer. The API turbidity requirement is 250 NTU, and prior to ballmill testing, the initial turbidity of the uncoated 100 mesh sandexceeded the API turbidity requirement of 250 NTU. During the ball milltesting, the turbidity of the uncoated 100 mesh sand nearly tripledafter 30 minutes. After 60 minutes of ball milling, the turbidity of theuncoated 100 mesh sand was nearly five times the initial turbidity.Examples 3 and 11 are exemplary in that the turbidity remains relativelylow even after being subjected to the ball mill test for 60 minutes. Thesecond group of data results labeled; UCS, showed whether the examplewould consolidate under conditions explained earlier in section;Unconfined Compressive Strength. If the sample consolidated you couldpossibly conclude that the sample might demonstrate particle to particlebonding.

Example 6. Performance of Chemicals of this Invention on Dust Control

Preparation of sample: a sample manufactured by the same procedure as inexample 1 with (50% in ethoxytriglycol) was used for the performancetest. In this test, the dust amount generated by the samples (coated anduncoated) in a designated test protocol will be recorded by a using aDustTrak™ dust meter, commercially available from TSI incorporated ofShoreview, Minn.

Multiple coated sands were made using 100 mg, and 50 mg, and 0 mg of theabove industrial sample. The coated sands were made by adding the aboveamounts to sand (100 g, 40/70 Unimin white sand) to give 0.10 wt. %,0.050 wt. %, and 0.00 wt. % level of coating respectively. The coatedsamples were prepared by manually mixing the chemical with the sand for5 min with a spatula. The samples were then tested in a dust meter(DustTrak™ dust meter from TSI) as shown in Table 4 below.

TABLE 4 Sucking flow rate Sucking flow rate 0.75 L/min 0.5 L/minCoating, wt. % Dust amount μg/m³ Dust amount μg/m³ 0 620 805 0.05 44.436 0.1 20.2 11

In this test, the dust meter continuously sucks dust-containing aircontaining the sample from a container and a dropping pipe. Here twoflow rates (0.75 L/min, 0.5 L/min) were employed for the test. The dustamount in the sucked air is read by the meter as micro gram per cubicmeter. As one can see from Table 4, even at 0.05% coating level, thecomposition reduces the dust level ten folds at both sucking flow rate.

Example 7: Flow-Back Control Proppant Pack Failure Flow Rate Test

This following example was performed by the API standard test Flow BackTest 400-16-12-15-02-F, with the following procedure.

The coating sample was prepared in the following manner: a coatingcomposition: 8 g of a selected adhesive made by using the typicalsynthetic procedure in Example 1 by replacing TOFA with S-rosin (CASnumber 8050-09-7), was dissolved in 8 g solvent (2 g Aromatic 150(ExxonMobil) plus 6 g ethoxytriglycol (Dow)). The sand sample was coatedat 1.5 wt. % level with the resulting composition. The coated sand andthe uncoated sand were then subject to the following test.

The flow back conductivity cell is loaded per ISO 13503-5 procedures.The zero-pack width is measured and recorded. The flow back conductivitycell is placed onto the press and the closure stress is increased to1,000 psi. The temperature was increased to 90° F. to allow the resincoated sand to cure for 24 hours. After the 24-hour period was complete,Nitrogen flow begins to remove any fluid from the cell and to ensurethat the proppant pack is dry. The Nitrogen Flow is then stopped and theend slot is removed to allow the sand to flow out of the flow back cell.The flow of Nitrogen is resumed beginning at 10 L/min and increased 10I/min until proppant pack failure occurs (proppant comes out of thecell). This same process is repeated for the 40/70 frac sand.

The coated sand having 1.5 wt. % of adhesive composition, exhibited afailure flow rate at 0.0566 lbs/min nitrogen, while the raw sandexhibited a failure flow rate at 0.0075 lbs/min nitrogen. This exampleillustrates that the composition herein demonstrated a 7.5 timesimprovement over the uncoated sand.

Example 8: Compatibility Test

The sample to be tested is the material made in Example 1 prepared asfollows. In a glass beaker, 1.0 g ethylene-vinylacetate copolymer (EVA,EVA 2850A from Celanese) and 1.0 g of the sample were heated to 120° C.,and mixed manually with a spatula for 5 min. After cooled to roomtemperature, the mixed sample-EVA product (1:1 ratio) was brokenmanually. About 60 mg of the mixed sample-EVA product was used to run athermal mechanic analysis (TMA) test along with an unmodified sample,and the EVA material. The TMA tests were done on a TA Q400 thermalmechanical analysis instrument. The heating procedure is: equilibrium at25 C for 5 min—heating at 10° C./min rate until 200° C. EVA is a typicalbinder for hot melt adhesive.

The TMA test records the mechanic strength under heating condition. Whenthere is phase transition, the sample will show mechanic strengthchange, and the machine will detect the change. It can accurately definethe phase transitions at the temperature range of the test. Therefore,if two materials are not dissolved by each other, they will show theirown phase transitions, which means they are not compatible. If twomaterials are dissolved by each other, they will form a homogenoussystem at molecular level, and the resulting material will have phasetransitions different from their original compositions. So if twomaterials are mixed, and the TMA doesn't their original phasetransitions, it means they form homogeneous new materials, in otherwords, the components are compatible. The non-mixed materials were alsotested.

Once a phase transition occurs, the curve will show an absorption peak.If there is another phase transition, it will show another absorptionpeak. If the two materials are not blended in molecular level, therewill be multi-phases that have different thermal mechanical properties,and they will show phase transition at different temperature. If onlyone transition temperature is observed, and the temperature is differentfrom any of the original temperature of the original components, thatmeans a new phase is formed at molecular level. The tackifier serves assolvent for the polymer binder (normally poor mobility due to highmolecular weight), provides tackiness (stickiness) for the adhesives,and help improve the wettability of the adhesive. So a tackifier isnormally small molecular compound with high softening point, andstickiness

An analysis of the TMA test illustrates there is only one phasetransition, and the indication of only one phase transition clearlydemonstrates that the two products have molecular level blending,forming a homogeneous solution. In other words, they are completelycompatible, and compatibility is the base for a compound to be atackifier.

Example 9: Pressure Sensitive Adhesive Properties Test

Pressure sensitive adhesive properties of viscoelastic materials wereevaluated by a special method that was developed for this purpose. Inthe test force as a function of time is measured for acompression/retraction type technique to evaluate pressure sensitiveadhesive properties. A portion of Sample 11 was heated to 120° C. andpoured onto a 100 mm think glass plate as substrate, which was clampedto the pedestal of a Brookfield CT3 Texture Analyzer, equipped with a 21mm diameter aluminum probe. The instrument was programmed to lower theprobe at a rate of 0.02 mm s⁻¹ onto the sample and to hold position fora period of 10 seconds, as soon as a force of 1 Newton is registered andthen to pull the probe from the sample at a rate of 0.5 mm s⁻¹. Theinitial gradual increase in force is associated with the probeapproaching the sample surface to make contact with increasing force upto the target value of 1N, where it holds position for 10 seconds. Bothsurfaces of the aluminum probe and glass substrate are fully wetted bythe sample at this stage, before the probe is retracted from theadhesive junction. The maximum force at break is used as quantitativeindication of adhesive properties, compared with the initial appliedforce. The onset of the retraction step is noted by the fast increase innegative force which ends at the failure point at −7.6N at approximately145 seconds, where the high negative force decline to a zero force valueover a short additional distance of movement as the adhesive sample ispulled apart in strings. Subsequent inspection of the probe andsubstrate surfaces showed a cohesive failure mechanism with bothsurfaces equally wetted with sample residue.

From the test, the “negative force” is indicative of adhesive action,and an increasing measured negative force indicates increasingperformance as adhesive. Also the ratio of (−7.6:1) of maximum tensionobserved to original force applied is indicative of PSA performance withhigher ratios indicating increasing PSA performance. Having the tensionat break exceeding the original pressure applied to an approximate 7times (7.6:1); is indicative of a very good pressure sensitive adhesive.The observation of a negative force indicates adhesion/“stickiness” andhigher forces at break (maximum negative force) indicate improvingadhesive performance, which is also referred to as “adhesive force”.Additionally, the ratio of input pressure applied; compared to tension(force at break) observed is an additional indication of pressuresensitive adhesive performance. A high tension at break as result of alow applied pressure indicates high performance as a pressure sensitiveadhesive. On the other hand; if a high applied pressure results in a lowobserved tension at break; this will be low/poor performance PSA. Thusthe example shows that the adhesive composition is a pressure sensitiveadhesive and also indicates high performance as a pressure sensitiveadhesive.

While the foregoing is directed to embodiments of the presentdisclosure, other and further embodiments of the disclosure may bedevised without departing from the basic scope thereof, and the scopethereof is determined by the claims that follow.

What is claimed is:
 1. A material comprising: a substrate; and anadhesive composition disposed on the substrate, wherein the adhesivecomposition comprises: a reaction product of: a diglycidyl ether or apolyacid selected from the group consisting of an aromatic polyacid, analiphatic polyacid, an aliphatic polyacid with an aromatic group, andcombinations thereof; and a polyamine; and one or more compoundsselected from the group consisting of a branched aliphatic acid havingC2-C26 alkyl group, a cyclic aliphatic acid with C7-C30 cyclic aliphaticgroup, a linear aliphatic acid having C2-C26 alkyl group, andcombinations thereof.
 2. The material of claim 1, wherein the adhesivecomposition further including one or more additives selected from thegroup consisting of coupling agents, consolidation agents, cross-linkingagents, and combinations thereof.
 3. The material of claim 1, whereinthe substrate is an organic or inorganic particulate material.
 4. Thematerial of claim 1, wherein the substrate is a dust source substrateselected from the group consisting of coal, mined materials, surfacemines, roads and road surfaces, mining waste dumps, manufacturing wastedumps, harvested and non-harvested agricultural crops, fields, charcoal,sand mines, sand transloads, proppant transloads, sand storage, proppantstorage, earth moving operations, cements, open railcar loads, opentruck loads, environmental remediation, quarries, mining waste, winderosion protection, agriculture product control, soil, and combinationsthereof.
 5. The material of claim 1, wherein the reaction productcomprises: from about 14 wt. % to about 75 wt. % of the polyacid of thecomposition; and from about 15 wt. % to about 45 wt. % polyamine of thecomposition; and from about 25 wt. % to about 65 wt. % of one or morecompounds selected from the group consisting of a branched aliphaticacid having C2-C26 alkyl group, a cyclic aliphatic acid with C7-C30cyclic aliphatic group, a linear aliphatic acid having C2-C26 alkylgroup, and combinations thereof, wherein the total wt. % of thecomposition is 100 wt. %.
 6. The material of claim 1, wherein theadhesive composition is modified by one or more processes comprising: a)grafting the backbone through oxyalkylation of the secondary amine, orthe hydroxyl group with ethylene oxide, propylene oxide or butyleneoxide in any ratio, or sequences, or molar mass; b) grafting thebackbone by reacting the secondary amine, or hydrocy with epoxides suchas alkylglycidyl ether such as butylglycidyl ether; p-tert-butyl phenylglycidyl ether, Cresyl hlycidyl ether, Castor oil glycidyl ether,glycidyl ester of neodecanoic acid; c) grafting the main chain throughamidation of the secondary amine, or through the esterification of thehydroxyl with carboxylic acids such as tall oil fatty acid, tallow fattyacid or versatic acid; d) quaterizing the secondary amine with benzylchloride, acrylic acid, etc.; or e) oxidizing the secondary amine toamine oxides.
 7. The material of claim 1, wherein the adhesivecomposition further comprises a solvent selected from the groupconsisting of aromatic solvents, ethers, alcohols, and water.
 8. Agravel pack particle comprising the material of claim
 1. 9. A method forapplying an adhesive composition, comprising: providing the adhesivecomposition, comprising a reaction product of: a diglycidyl ether or apolyacid selected from the group consisting of an aromatic polyacid, analiphatic polyacid, an aliphatic polyacid with an aromatic group, andcombinations thereof; and a polyamine; and one or more compoundsselected from the group consisting of a branched aliphatic acid havingC2-C26 alkyl group, a cyclic aliphatic acid with C7-C30 cyclic aliphaticgroup, a linear aliphatic acid having C2-C26 alkyl group, andcombinations thereof; providing a substrate having an exposed surface;and applying the adhesive composition to the exposed surface of thesubstrate.
 10. The method of claim 9, wherein the substrate is anorganic or inorganic particulate material.
 11. The method of claim 9,wherein the substrate is a dust source substrate selected from the groupconsisting of coal, mined materials, surface mines, roads and roadsurfaces, mining waste dumps, manufacturing waste dumps, harvested andnon-harvested agricultural crops, fields, charcoal, sand mines, sandtransloads, proppant transloads, sand storage, proppant storage, earthmoving operations, cements, open railcar loads, open truck loads,environmental remediation, quarries, mining waste, wind erosionprotection, agriculture product control, soil, and combinations thereof.12. The method of claim 9, wherein the reaction product comprises: fromabout 14 wt. % to about 75 wt. % of the polyacid of the composition; andfrom about 15 wt. % to about 45 wt. % polyamine of the composition; andfrom about 25 wt. % to about 65 wt. % of one or more compounds selectedfrom the group consisting of a branched aliphatic acid having C2-C26alkyl group, a cyclic aliphatic acid with C7-C30 cyclic aliphatic group,a linear aliphatic acid having C2-C26 alkyl group, and combinationsthereof, wherein the total wt. % of the composition is 100 wt. %. 13.The method of claim 9, wherein the adhesive composition is modified byone or more processes comprising: a) grafting the backbone throughoxyalkylation of the secondary amine, or the hydroxyl group withethylene oxide, propylene oxide or butylene oxide in any ratio, orsequences, or molar mass; b) grafting the backbone by reacting thesecondary amine, or hydrocy with epoxides such as alkylglycidyl ethersuch as butylglycidyl ether; p-tert-butyl phenyl glycidyl ether, Cresylhlycidyl ether, Castor oil glycidyl ether, glycidyl ester of neodecanoicacid; c) grafting the main chain through amidation of the secondaryamine, or through the esterification of the hydroxyl with carboxylicacids such as tall oil fatty acid, tallow fatty acid or versatic acid;d) quaterizing the secondary amine with benzyl chloride, acrylic acid,etc.; or e) oxidizing the secondary amine to amine oxides.
 14. Themethod of claim 9, wherein the adhesive composition further comprises asolvent selected from the group consisting of aromatic solvents, ethers,alcohols, and water.